Achieving consecutive flattening and dendrite-free deposition for the zinc anodes is essential to avoid internal short circuits or premature failure in the Zn-ion hybrid supercapacitor (ZHSC), which largely depends on the crystal growth during the electrocrystallization process. Herein, the tetrapropyl ammonium bromide additive was employed to reconstruct the inner Helmholtz plane (IHP) structure for manipulating the Zn deposition behavior and stabilizing the interfacial electrochemistry. Joint experimental and theoretical results show that electrophilic quaternary ammonium cations (TPA+) provoke the linkage effect after the specifical adsorption at IHP of the Zn electrode, which includes the molecular/ion distribution regulation, electrostatic shielding effect, crystallographic optimization, and solid electrolyte interphase (SEI) layer formation. The adsorbed TPA+ cations at IHP expel SO42− anions, bringing a reconfiguration of the ion/molecule distribution, which leads to a relatively uniform Zn2+ions distribution at electrode/electrolyte interface and a sluggish electroreduction reaction kinetics. Meanwhile, the electrostatic shielding effect regulates the crystallographic energetic preference of Zn deposits and induces the stratiform Zn growth and dominant Zn (002) texture. Concomitantly, the partial interfacial adsorbed TPA+ cations were electrochemically reduced to form the inorganic-organic hybrid SEI layer to further enhance the corrosion resistance and stability of the Zn electrode. Consequently, TPA+ cations mediated electrolyte enables Zn||Zn cells to exhibit a reversible plating/stripping performance for more than 2800 h. Additionally, a long-term cycling life can be obtained in the Zn||activated carbon ZHSC with this electrolyte. The electrolyte mediation strategy to realize the complementary interface effect and crystalline optimization provides promising feasibility on highly reversible Zn anodes.